US4662944A - Process and composition for sensitizing articles for metallization - Google Patents
Process and composition for sensitizing articles for metallization Download PDFInfo
- Publication number
- US4662944A US4662944A US05/753,320 US75332076A US4662944A US 4662944 A US4662944 A US 4662944A US 75332076 A US75332076 A US 75332076A US 4662944 A US4662944 A US 4662944A
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- US
- United States
- Prior art keywords
- metal
- medium
- water
- solution
- deposition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 238000000034 method Methods 0.000 title description 14
- 230000008569 process Effects 0.000 title description 11
- 239000000203 mixture Substances 0.000 title description 9
- 230000001235 sensitizing effect Effects 0.000 title description 5
- 238000001465 metallisation Methods 0.000 title description 2
- 150000002500 ions Chemical class 0.000 claims abstract description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 9
- 239000000758 substrate Substances 0.000 claims description 8
- 239000012736 aqueous medium Substances 0.000 claims description 3
- 238000007772 electroless plating Methods 0.000 claims 1
- 238000002360 preparation method Methods 0.000 claims 1
- 230000037452 priming Effects 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 abstract description 29
- 239000002184 metal Substances 0.000 abstract description 27
- 230000008021 deposition Effects 0.000 abstract description 10
- 230000001464 adherent effect Effects 0.000 abstract description 4
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 25
- 239000000243 solution Substances 0.000 description 21
- 239000002609 medium Substances 0.000 description 19
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 15
- 239000003638 chemical reducing agent Substances 0.000 description 13
- 150000001875 compounds Chemical class 0.000 description 13
- -1 i.e. Substances 0.000 description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 12
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000010949 copper Substances 0.000 description 12
- 229910052802 copper Inorganic materials 0.000 description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- 238000000151 deposition Methods 0.000 description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000000454 electroless metal deposition Methods 0.000 description 6
- 239000010970 precious metal Substances 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 239000000080 wetting agent Substances 0.000 description 6
- 239000005749 Copper compound Substances 0.000 description 5
- 150000001880 copper compounds Chemical class 0.000 description 5
- 238000007654 immersion Methods 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 239000012279 sodium borohydride Substances 0.000 description 5
- 229910000033 sodium borohydride Inorganic materials 0.000 description 5
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 description 4
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 4
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 206010070834 Sensitisation Diseases 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 3
- 239000010953 base metal Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 3
- 150000002739 metals Chemical group 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 2
- 229910000085 borane Inorganic materials 0.000 description 2
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 description 2
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 2
- 150000004696 coordination complex Chemical class 0.000 description 2
- 229960003280 cupric chloride Drugs 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical class [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000008313 sensitization Effects 0.000 description 2
- 235000011006 sodium potassium tartrate Nutrition 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000001119 stannous chloride Substances 0.000 description 2
- 235000011150 stannous chloride Nutrition 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 2
- YIROYDNZEPTFOL-UHFFFAOYSA-N 5,5-Dimethylhydantoin Chemical compound CC1(C)NC(=O)NC1=O YIROYDNZEPTFOL-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VMQMZMRVKUZKQL-UHFFFAOYSA-N Cu+ Chemical compound [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 241000872198 Serjania polyphylla Species 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 238000010420 art technique Methods 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- FTDUHBOCJSQEKS-UHFFFAOYSA-N borane;n-methylmethanamine Chemical class B.CNC FTDUHBOCJSQEKS-UHFFFAOYSA-N 0.000 description 1
- 229960000359 chromic chloride Drugs 0.000 description 1
- 150000001844 chromium Chemical class 0.000 description 1
- LJAOOBNHPFKCDR-UHFFFAOYSA-K chromium(3+) trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Cl-].[Cr+3] LJAOOBNHPFKCDR-UHFFFAOYSA-K 0.000 description 1
- 235000007831 chromium(III) chloride Nutrition 0.000 description 1
- 239000011636 chromium(III) chloride Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000012612 commercial material Substances 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- KPVWDKBJLIDKEP-UHFFFAOYSA-L dihydroxy(dioxo)chromium;sulfuric acid Chemical compound OS(O)(=O)=O.O[Cr](O)(=O)=O KPVWDKBJLIDKEP-UHFFFAOYSA-L 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910001867 inorganic solvent Inorganic materials 0.000 description 1
- 239000003049 inorganic solvent Substances 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000005340 laminated glass Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 150000002816 nickel compounds Chemical class 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000005488 sandblasting Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- IUTCEZPPWBHGIX-UHFFFAOYSA-N tin(2+) Chemical compound [Sn+2] IUTCEZPPWBHGIX-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1603—Process or apparatus coating on selected surface areas
- C23C18/1605—Process or apparatus coating on selected surface areas by masking
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
- C23C18/2046—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment
- C23C18/2073—Multistep pretreatment
- C23C18/208—Multistep pretreatment with use of metal first
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/28—Sensitising or activating
- C23C18/285—Sensitising or activating with tin based compound or composition
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material
- H05K3/181—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating
Definitions
- This invention relates to process and compositions for sensitizing articles to the deposition of metals from solutions thereof. More particularly, it relates to improved means to provide adherent metal layers on non-metallic articles by treating such articles with a series of media which deposit catalytically active elements or precursors and contacting with electroless metal deposition solutions.
- Sensitizing non-metallic substrates to the deposition of electroless metal is a key step in the production of decorative and industrially useful metallized objects, such as name plates, dials, printed circuits, and the like.
- This sensitization is conventionally carried out by treating the substrate either stepwise with precious metal, e.g., palladium or platinum, ions in solution followed by a solution of stannous tin or similar ions, or all in one step with a unitary colloidal suspension of precious metal or with a solution complex of precious metal ion, stannous ion and an anion.
- precious metal e.g., palladium or platinum, ions in solution followed by a solution of stannous tin or similar ions, or all in one step with a unitary colloidal suspension of precious metal or with a solution complex of precious metal ion, stannous ion and an anion.
- Bernhardt et al. U.S. Pat. No. 3,547,784 disclose treating a nonmetallic surface with stannous salt when with a silver salt and then electrolessly plating using processes and deposition baths for copper, nickel and silver found, for example, in Schneble, Jr. et al., U.S. Pat. Nos. 3,527,215 and 3,347,724.
- the Bernhardt et al process is conventional and the point of novelty resides in using a particular copolymer of vinyl chloride, which was not easy to metallize up until the time of the invention.
- metal reduction sensitizers which can employ base metal ions, followed by treatment with reducing solutions or radiant energy, e.g., heat, light and the like, to produce the sensitized surface.
- the metal reduction sensitizing process consists of coating a surface, preferably one which has been activated in known ways either to render it permanently polarized and wettable, or microporous, with a reducible metal salt solution, e.g., CuSO 4 .5H 2 O, NiSO 4 .6H 2 O, and the like, then either draining, semi-drying or completely drying the so-treated surface. Sensitization is then completed by immersing the surface into a strongly reducing medium, e.g., a sodium borohydride solution, during which step the metal salts are reduced to elemental metal particles. This sensitized surface is then rinsed and electrolessly plated.
- a strongly reducing medium e.g., a sodium borohydride solution
- improvements are provided in the wettability and adsorptivity of metal compound media which are used to render surfaces sensitive to electroless metal depositions. Because of their improved wettability and adsorptivity, such compositions can be formulated from base metals or combinations thereof with precious metals which have performance comparable to traditional expensive and somewhat unstable entirely precious metal-based sensitizers.
- a process for sensitizing a nonmetallic article for the deposition of adherent metal from an electroless metal deposition solution in contact therewith comprising:
- step (iii) simultaneously with or subsequently to step (ii) treating said surface with one or more agents, if necessary, to transfer said element or combination of elements into a state which is catalytically active for the deposition of electroless metal.
- the agent or agents in step (iii) will be reducing agents, such as borohydrides, e.g., alkali metal borohydrides, amine boranes, e.g., dimethylamine boranes, hydrazine hydrate, and others. If difficulty metallizable substrates are used, e.g., acrylonitrile-butadienestyrene (ABS) polymers, in preferred embodiments step (iii) will be carried out in two separate stages and employing two separate reducing agents.
- borohydrides e.g., alkali metal borohydrides
- amine boranes e.g., dimethylamine boranes, hydrazine hydrate, and others.
- difficulty metallizable substrates e.g., acrylonitrile-butadienestyrene (ABS) polymers
- step (iii) will be carried out in two separate stages and employing two separate reducing agents.
- the first reducing agent will be a so-called secondary reducer, e.g., formalkehyde, a formaldehyde precursor, dimethyl hydantoin, a stabilized form thereof, and the like
- the second reducing agent will be a strong, primary reducer, e.g., a borohydride or an amine borane.
- the element or combination of elements are base metal elements, preferably, copper, nickel, cobalt, iron or mixtures of any of the foregoing.
- base metal elements preferably, copper, nickel, cobalt, iron or mixtures of any of the foregoing.
- molybdenum, vanadium, and leads or mixtures thereof with any of the preferable elements cited above may also be used.
- the compound or combination of compounds in the first medium will be a wetting agent, i.e., it will seek and affix itself firmly to the surface being treated, e.g., by electrical attraction or other means.
- the first or second medium will comprise a wetting agent having a polarity which is opposite to the polarity of at least some of the surface sites of the article to be sensitized.
- the present invention also contemplates the novel compositions having the required characteristics, e.g., media including compounds or combinations which are adsorbable, transformable, if necessary, and removable in excess by a second medium, as set forth above.
- a first medium is formed when a copper compound or a nickel compound or mixture thereof is mixed with ammonia or amine to form a copper or nickel complex with ammonia or amine or a mixture thereof.
- ammonia or amines in their own rights powerful wetting agents, but so are the formed ion complexes. It appears that such ion complexes behave much like quaternary ammonium complexes, i.e., cationically.
- Such positively charged (polar) ion complexes are adsorbed by negative surface sites on the article to be sensitized.
- the rinse of the base with a second medium will decrease the solubility of the compound or combination of compounds.
- the basic metal ammonium compound is formed; in the cuprous ion complex case, loss of HCl in the rinse will lead to decreased solubility.
- the second medium rinse causes decreased solubility.
- the media can comprise organic and inorganic solvents such as water, alcohols, e.g., methanol and the like, ketones, e.g., acetone, methyl ethyl ketone, etc., esters, e.g., ethyl acetate.
- organic and inorganic solvents such as water, alcohols, e.g., methanol and the like, ketones, e.g., acetone, methyl ethyl ketone, etc., esters, e.g., ethyl acetate.
- aqueous media are used.
- Media based on organic systems can be employed, particularly on resin bearing systems such as epoxy.
- cupric chloride is readily dissolved and complexed with dimethyl formamide (DMF).
- a resin bearing surface brought into contact with this solution quickly adsorbs metal complex.
- the surface is then rinsed with a second medium, e.g., water, which removes excess metal complex (and first medium) and then the surface is next treated with an agent to convert the metal to a catalytically active state, such as a solution of sodium borohydride or hydrazine hydrate dissolved in a suitable solvent, such as DMF.
- a catalytically active state such as a solution of sodium borohydride or hydrazine hydrate dissolved in a suitable solvent, such as DMF.
- the present invention can be used to sensitize a wide variety of non-metallic substrates, such as plastic, e.g., polyepoxides, phenolics, polystyrene, polyesters, nylons, polyacetals, polycarbonates, and the like, or glass, porcelain, cloth, paper, compressed wood, and the like.
- ABS resins are especially efficiently metallized with a "two-stage" treatment with reducing agents, as described above and exemplified hereinafter.
- the resinous substrates can be treated in known ways to activate the surfaces prior to sensitization--this gives the highest adhesion between subsequently deposited electroless metal and the resinous substrates.
- One way to activate resinous bases is to render them permanently polar and wettable by treatment first with a preactivating agent, e.g., dimethyl formamide, dimethyl sulfoxide, methyl ethyl ketone or mixture of toluene and water, etc., depending on the nature of the resin, then with an activator such as chromic acid-sulfuric acid, and then with a reducing agent, such as sodium bisulfite or hydroxylamine hydrochloride, the result of which is to produce a permanently polarized, wettable surface.
- a preactivating agent e.g., dimethyl formamide, dimethyl sulfoxide, methyl ethyl ketone or mixture of toluene and water, etc.
- an activator such as chromic acid-sulfuric acid
- a reducing agent such as sodium bisulfite or hydroxylamine hydrochloride
- the surface of the resinous article can be partially degradable, or be provided with a surface layer having such properties, or contain degradable particles, such as rubber particles, and on treatment with suitable agents, such as chromic acid, or permanganate, is caused to become microporous and thus activated to adherent metal deposits.
- any conventional electroless metal deposition bath useful with conventionally precious metal sensitized surfaces can be used to deposit metal on the surfaces sensitized according to this invention.
- the deposition baths will contain an ion of the metal or metals whose deposition is desired, a complexing agent for the ion, a reducing agent for the ion and an agent to adjust the bath to an optimum, predetermined pH.
- Such baths are amply described in the patent and textbook literature. See, for example, the patents cited hereinabove.
- An epoxy-glass laminate is provided with holes at pre-selected locations.
- the surface is rendered permanently polarized and wettable by immersion in dimethyl formamide at 80° F. for 2-5 minutes, rinsing in water, immersing in a solution of 100 g./l. CrO 3 , 250 ml./l. of concentrated sulfuric acid, balance water, for about 1 minute, immersing in a 5% solution of NaHSO 3 for about 2 minutes, rinsing thoroughly in cold water, then in hot (160° F.) water and air or oven-drying.
- the so-treated laminate is next rinsed thoroughly with a second medium comprising cold water to decrease the solubility of said copper compound and to remove the excess.
- the laminate is next immersed in a water or methanol solution of 1 gram/liter of sodium borohydride, causing the adsorbed copper compound to be reduced to catalytic sites of elemental copper.
- the sensitized laminate is transferred to an electroless copper deposition bath of the formula:
- the conductor pattern is built up to the desired thickness, the mask is removed, and the finished printed circuit board is post cured for 30 minutes at about 320° F.
- This example illustrates the use of two separate reducers in the process of the present invention.
- ABS acrylonitrile-butadiene-styrene terpolymer
- Alkaline cleaner 65° C.
- Oakite 90 or Altrex are illustrative of suitable commercial materials and trisodium phosphate is also suitable.
- the cleaned ABS disc is rinsed for 5 minutes in water, then the surface is rendered permanently polarized and wettable by immersion for 1 minute in a solution of 250 ml./l. of methyl ethyl ketone in water, rinsing in water for 3-5 minutes, immersing in a solution of 370 g./l. of chromic acid, 185 ml./l. of concentrated sulfuric acid, 0.5 g./l.
- the so-treated disc is rinsed gently with water for 1 minute at pH (5-8) and about 15°-20° C. to decrease the solubility of the copper compound and to remove the excess.
- the disc is next immersed in a first reducer solution comprising
- the second reducer is made by adding the NaBH 4 to water and mixing for 5 minutes, then adding the NaOH and mixing for 5 minutes longer).
- the disc which now has catalytic surface sites of elemental copper is rinsed for 2 minutes with water (pH 5.0-8.0).
- the sensitized disc is transferred to an electroless copper deposition bath of the formula:
- Electroless copper builds up to the desired thickness.
- the invention is not limited to printed circuit boards or to the specific steps and methods described. Moreover, electroless metal baths for depositing any other conventional metal than copper, e.g., nickel, cobalt, silver, gold, and the like, can be used.
Abstract
Non-metallic articles are sensitized for deposition of adherent metal from electroless metal solutions in contact therewith by treatment with a first medium including cuprous ions and stannous ions thereby absorbing on the surface in situ at least said cuprous ions; thereafter treating the surface with a second medium to decrease the solubility of the cuprous ions and/or simultaneously removing the excess; and simultaneously or subsequently, if necessary, treating the surface with one or more agents to transfer said cuprous ions into a catalytically-active state.
Description
This application is a division of application Ser. No. 632,700, filed Nov. 17, 1975, now abandoned, as a continuation of application Ser. No. 407,555, filed Oct. 18, 1973, now abandoned, in turn a continuation-in-part of application Ser. No. 270,861, filed July 11, 1972, now abandoned.
This invention relates to process and compositions for sensitizing articles to the deposition of metals from solutions thereof. More particularly, it relates to improved means to provide adherent metal layers on non-metallic articles by treating such articles with a series of media which deposit catalytically active elements or precursors and contacting with electroless metal deposition solutions.
Sensitizing non-metallic substrates to the deposition of electroless metal, e.g., Group IB and VIII metals, i.e., copper, cobalt, nickel, gold, silver and the like, is a key step in the production of decorative and industrially useful metallized objects, such as name plates, dials, printed circuits, and the like. This sensitization is conventionally carried out by treating the substrate either stepwise with precious metal, e.g., palladium or platinum, ions in solution followed by a solution of stannous tin or similar ions, or all in one step with a unitary colloidal suspension of precious metal or with a solution complex of precious metal ion, stannous ion and an anion. This produces a sensitive surface which when immersed in a conventional electroless metal deposition bath causes metal to deposit on all of the sensitized areas thereof.
A number of proposals have been made to carry out such processes more economically and efficiently:
Chiecchi, U.S. Pat. No. 3,379,556 discloses immersion in a beta resorcylato chromic chloride solution to eliminate pretreatments such as sealing, sandblasting, etching and the like. This method still requires the use of a two step, stannous-palladium subsequent treatment, see, for example, Schneble, Jr. et al., U.S. Pat. No. 3,403,035 and U.S. Pat. No. 3,033,703. Moreover, the Werner-type chromium complexes are difficult to prepare, stabilize and use. In addition, the complex must be polymerized after application and before subsequent treatment steps.
Bernhardt et al., U.S. Pat. No. 3,547,784 disclose treating a nonmetallic surface with stannous salt when with a silver salt and then electrolessly plating using processes and deposition baths for copper, nickel and silver found, for example, in Schneble, Jr. et al., U.S. Pat. Nos. 3,527,215 and 3,347,724. The Bernhardt et al process is conventional and the point of novelty resides in using a particular copolymer of vinyl chloride, which was not easy to metallize up until the time of the invention.
In a more recent developement, there have been provided the so-called metal reduction sensitizers, which can employ base metal ions, followed by treatment with reducing solutions or radiant energy, e.g., heat, light and the like, to produce the sensitized surface.
The metal reduction sensitizing process consists of coating a surface, preferably one which has been activated in known ways either to render it permanently polarized and wettable, or microporous, with a reducible metal salt solution, e.g., CuSO4.5H2 O, NiSO4.6H2 O, and the like, then either draining, semi-drying or completely drying the so-treated surface. Sensitization is then completed by immersing the surface into a strongly reducing medium, e.g., a sodium borohydride solution, during which step the metal salts are reduced to elemental metal particles. This sensitized surface is then rinsed and electrolessly plated.
Because thorough rinsing of excess metal salts before transferring the workpiece to the reducing medium cannot be practiced, there are numberous difficulties when dealing with copper clad surfaces (on other portions of the article). Rinsing usually removes all of the metal salts. Moreover, there is also the problem of drag-over of excess metal salts into the reducing medium, and this shortens its life and also turns it black with atomic metal particles.
Obviously, if a means could be provided to rinse excess and unwanted metal salts from the surface before immersion in the reducing medium, the above noted problems would be avoided. In addition, control will be facilitated because rinsing will provide a positive indication that only those final catalytic elemental particles which remain are those which are adsorbed by the surface.
According to the present invention, improvements are provided in the wettability and adsorptivity of metal compound media which are used to render surfaces sensitive to electroless metal depositions. Because of their improved wettability and adsorptivity, such compositions can be formulated from base metals or combinations thereof with precious metals which have performance comparable to traditional expensive and somewhat unstable entirely precious metal-based sensitizers.
In comparison with the prior art techniques, the instant system provides the following distinct advantages:
(i) more complete rinsing between the first medium and any subsequent transformation agent can now be tolerated because of tremendously improved adsorption of any metallic compound or element in the first medium to the surface;
(ii) "take" or coverage in the electroless metal bath is wholly uniform and rapid; and
(iii) in the case of activated substrates, metallization within the surface micropores is deep and complete enhancing bond strength.
According to the present invention, there is provided a process for sensitizing a nonmetallic article for the deposition of adherent metal from an electroless metal deposition solution in contact therewith, said process comprising:
(i) treating the surface or selected areas of the surface of said article with a first medium comprising a compound or combination of compounds containing an element which in one of its states is catalytically active to electroless metal deposition or a combination of such elements thereby adsorbing on said surface in situ the said element or elements, or a compound or compounds containing said element or elements;
(ii) thereafter treating said article with a second medium to decrease the solubility of said compound or combination of compounds and/or simultaneously removing unadsorbed and excess components of said first medium from said surface; and
(iii) simultaneously with or subsequently to step (ii) treating said surface with one or more agents, if necessary, to transfer said element or combination of elements into a state which is catalytically active for the deposition of electroless metal.
In a preferred feature of the invention, the agent or agents in step (iii) will be reducing agents, such as borohydrides, e.g., alkali metal borohydrides, amine boranes, e.g., dimethylamine boranes, hydrazine hydrate, and others. If difficulty metallizable substrates are used, e.g., acrylonitrile-butadienestyrene (ABS) polymers, in preferred embodiments step (iii) will be carried out in two separate stages and employing two separate reducing agents. In one such process, the first reducing agent will be a so-called secondary reducer, e.g., formalkehyde, a formaldehyde precursor, dimethyl hydantoin, a stabilized form thereof, and the like, and the second reducing agent will be a strong, primary reducer, e.g., a borohydride or an amine borane.
Among the features of this invention are processes wherein the element or combination of elements are base metal elements, preferably, copper, nickel, cobalt, iron or mixtures of any of the foregoing. Under certain circumstances, molybdenum, vanadium, and leads or mixtures thereof with any of the preferable elements cited above may also be used.
Preferably, the compound or combination of compounds in the first medium will be a wetting agent, i.e., it will seek and affix itself firmly to the surface being treated, e.g., by electrical attraction or other means. Preferably also, the first or second medium will comprise a wetting agent having a polarity which is opposite to the polarity of at least some of the surface sites of the article to be sensitized.
The present invention also contemplates the novel compositions having the required characteristics, e.g., media including compounds or combinations which are adsorbable, transformable, if necessary, and removable in excess by a second medium, as set forth above.
By way of further illustration, but with no intention of being bound by an hypothesis, in one embodiment, a first medium is formed when a copper compound or a nickel compound or mixture thereof is mixed with ammonia or amine to form a copper or nickel complex with ammonia or amine or a mixture thereof. Not only are ammonia or amines in their own rights powerful wetting agents, but so are the formed ion complexes. It appears that such ion complexes behave much like quaternary ammonium complexes, i.e., cationically. Such positively charged (polar) ion complexes are adsorbed by negative surface sites on the article to be sensitized.
In another embodiment a dichlorocuprate [I- ] ion complex:
[CuCl.sub.2.sup.-]H.sup.+
is formed by boiling copper chips with cupric chloride in a large excess of concentrated hydrochloric acid. As in the ammonia complex case, this compound is highly polar (polarity reversed however) and readily attaches to positive surface sites due to its relatively negative charge.
In these embodiments, the rinse of the base with a second medium will decrease the solubility of the compound or combination of compounds. In the metal ammonium complex case, the basic metal ammonium compound is formed; in the cuprous ion complex case, loss of HCl in the rinse will lead to decreased solubility. In the soluble iron salt case, the second medium rinse causes decreased solubility.
All three concepts can use a variety of metallic compounds.
The media can comprise organic and inorganic solvents such as water, alcohols, e.g., methanol and the like, ketones, e.g., acetone, methyl ethyl ketone, etc., esters, e.g., ethyl acetate. Preferably, aqueous media are used.
Media based on organic systems can be employed, particularly on resin bearing systems such as epoxy. In one such system, cupric chloride is readily dissolved and complexed with dimethyl formamide (DMF). A resin bearing surface brought into contact with this solution quickly adsorbs metal complex. The surface is then rinsed with a second medium, e.g., water, which removes excess metal complex (and first medium) and then the surface is next treated with an agent to convert the metal to a catalytically active state, such as a solution of sodium borohydride or hydrazine hydrate dissolved in a suitable solvent, such as DMF.
The present invention can be used to sensitize a wide variety of non-metallic substrates, such as plastic, e.g., polyepoxides, phenolics, polystyrene, polyesters, nylons, polyacetals, polycarbonates, and the like, or glass, porcelain, cloth, paper, compressed wood, and the like. ABS resins are especially efficiently metallized with a "two-stage" treatment with reducing agents, as described above and exemplified hereinafter. The resinous substrates can be treated in known ways to activate the surfaces prior to sensitization--this gives the highest adhesion between subsequently deposited electroless metal and the resinous substrates.
One way to activate resinous bases is to render them permanently polar and wettable by treatment first with a preactivating agent, e.g., dimethyl formamide, dimethyl sulfoxide, methyl ethyl ketone or mixture of toluene and water, etc., depending on the nature of the resin, then with an activator such as chromic acid-sulfuric acid, and then with a reducing agent, such as sodium bisulfite or hydroxylamine hydrochloride, the result of which is to produce a permanently polarized, wettable surface.
Such techniques are disclosed in greater detail, for example, in copending U.S. patent application Ser. No. 227,678, filed Feb. 18, 1972, now U.S. Pat. No. 4,405,923, the disclosure of which is incorporated herein by reference.
On the other hand, the surface of the resinous article can be partially degradable, or be provided with a surface layer having such properties, or contain degradable particles, such as rubber particles, and on treatment with suitable agents, such as chromic acid, or permanganate, is caused to become microporous and thus activated to adherent metal deposits.
Any conventional electroless metal deposition bath useful with conventionally precious metal sensitized surfaces can be used to deposit metal on the surfaces sensitized according to this invention. Generally, the deposition baths will contain an ion of the metal or metals whose deposition is desired, a complexing agent for the ion, a reducing agent for the ion and an agent to adjust the bath to an optimum, predetermined pH. Such baths are amply described in the patent and textbook literature. See, for example, the patents cited hereinabove.
The following examples illustrate the invention.
An epoxy-glass laminate is provided with holes at pre-selected locations. The surface is rendered permanently polarized and wettable by immersion in dimethyl formamide at 80° F. for 2-5 minutes, rinsing in water, immersing in a solution of 100 g./l. CrO3, 250 ml./l. of concentrated sulfuric acid, balance water, for about 1 minute, immersing in a 5% solution of NaHSO3 for about 2 minutes, rinsing thoroughly in cold water, then in hot (160° F.) water and air or oven-drying.
Then the laminate is reverse-masked with a conventional background resist and then sensitized by immersion in and adsorption of a copper compound from a first medium comprising
______________________________________ CuCl 10 g./l. HCl (conc.) 300 ml./l. stannous chloride.2H.sub.2 O 30 g./l. water (to make) ______________________________________
The so-treated laminate is next rinsed thoroughly with a second medium comprising cold water to decrease the solubility of said copper compound and to remove the excess.
The laminate is next immersed in a water or methanol solution of 1 gram/liter of sodium borohydride, causing the adsorbed copper compound to be reduced to catalytic sites of elemental copper.
The sensitized laminate is transferred to an electroless copper deposition bath of the formula:
______________________________________ CuSO.sub.4.5H.sub.2 O 30 g./l. Rochelle salts 150 g./l. sodium cyanide 30 mg./l. formaldehyde (37%) 15 ml./l. wetting agent 1 ml. sodium hydroxide to pH 13 water (to make) ______________________________________
The conductor pattern is built up to the desired thickness, the mask is removed, and the finished printed circuit board is post cured for 30 minutes at about 320° F.
This example illustrates the use of two separate reducers in the process of the present invention.
A disc of acrylonitrile-butadiene-styrene terpolymer (ABS) is immersed for 5 minutes in an alkaline cleaner at 65° C. Oakite 90 or Altrex are illustrative of suitable commercial materials and trisodium phosphate is also suitable. The cleaned ABS disc is rinsed for 5 minutes in water, then the surface is rendered permanently polarized and wettable by immersion for 1 minute in a solution of 250 ml./l. of methyl ethyl ketone in water, rinsing in water for 3-5 minutes, immersing in a solution of 370 g./l. of chromic acid, 185 ml./l. of concentrated sulfuric acid, 0.5 g./l. of fluorinated hydrocarbon wetting agent (3M Company, FC-95), balance water, for about 5-8 minutes, rinsing in water for 1 minute, immersing in a solution of hydroxyl-amine hydrochloride, 20 g./l., hydrochloric acid (37%), 200 ml./l., balance water, for about 2 minutes and rinsing thoroughly in water for 5 minutes.
Then the activated disc is immersed in a solution comprising
______________________________________ CuCl 10 g./l. HCl (conc.) 300 ml./l. stannous chloride.2H.sub.2 O 30 g./l. water (to make). ______________________________________
The so-treated disc is rinsed gently with water for 1 minute at pH (5-8) and about 15°-20° C. to decrease the solubility of the copper compound and to remove the excess.
The disc is next immersed in a first reducer solution comprising
______________________________________ formaldehyde (37%) 100 ml./l. water (to make) ______________________________________
for 1 minute, and the excess first solution is drained off for about 15-30 seconds.
Then the disc is immersed for 5 minutes in a second reducer solution comprising
______________________________________ sodium borohydride 1 g./l. sodium hydroxide (50%) 2 ml./l. deionized water (to make) ______________________________________
(The second reducer is made by adding the NaBH4 to water and mixing for 5 minutes, then adding the NaOH and mixing for 5 minutes longer).
The disc which now has catalytic surface sites of elemental copper is rinsed for 2 minutes with water (pH 5.0-8.0).
The sensitized disc is transferred to an electroless copper deposition bath of the formula:
______________________________________ CuSO.sub.4.5H.sub.2 O 30 g./l. Rochelle salts 150 g./l. sodium cyanide 30 mg./l. formaldehyde (37%) 15 ml./l. wetting agent 1 ml. sodium hydroxide to pH 13 water (to make) ______________________________________
Electroless copper builds up to the desired thickness.
The invention is not limited to printed circuit boards or to the specific steps and methods described. Moreover, electroless metal baths for depositing any other conventional metal than copper, e.g., nickel, cobalt, silver, gold, and the like, can be used.
Claims (2)
1. A solution useful in the priming of dielectric substrates in preparation for electroless plating comprising stannous and cuprous ions in aqueous media, said stannous to cuprous ions being present in said aqueous media in a molar ratio of about 1.3 to 1.
2. The solution of claim 1, wherein said solution includes hydrochloric acid.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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US05/753,320 US4662944A (en) | 1972-07-11 | 1976-12-22 | Process and composition for sensitizing articles for metallization |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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US27086172A | 1972-07-11 | 1972-07-11 | |
US40755573A | 1973-10-18 | 1973-10-18 | |
US05/753,320 US4662944A (en) | 1972-07-11 | 1976-12-22 | Process and composition for sensitizing articles for metallization |
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US63270075A Division | 1972-07-11 | 1975-11-17 |
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US4662944A true US4662944A (en) | 1987-05-05 |
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US05/753,320 Expired - Lifetime US4662944A (en) | 1972-07-11 | 1976-12-22 | Process and composition for sensitizing articles for metallization |
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GB2232168B (en) * | 1989-05-01 | 1993-06-16 | Enthone | Circuit boards |
US5498467A (en) * | 1994-07-26 | 1996-03-12 | W. L. Gore & Associates, Inc. | Process for preparing selectively conductive materials by electroless metal deposition and product made therefrom |
US5731073A (en) * | 1996-10-01 | 1998-03-24 | W. L. Gore & Associates, Inc. | Reusable, selectively conductive, Z-axis, elastomeric composite substrate |
US20040110374A1 (en) * | 2002-12-10 | 2004-06-10 | Enthone, Inc. | Copper activator solution and method for semiconductor seed layer enhancement |
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US2472393A (en) * | 1944-09-25 | 1949-06-07 | American Steel & Wire Co | Process and bath for copper coating ferrous metal |
US3674517A (en) * | 1970-07-23 | 1972-07-04 | Ppg Industries Inc | Solution for depositing transparent metal films |
US3682671A (en) * | 1970-02-05 | 1972-08-08 | Kollmorgen Corp | Novel precious metal sensitizing solutions |
US3725108A (en) * | 1969-03-05 | 1973-04-03 | Enthone | Chemical reduction metal plated diallylphthalate polymer and preparation process |
US3925578A (en) * | 1971-07-29 | 1975-12-09 | Kollmorgen Photocircuits | Sensitized substrates for chemical metallization |
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US2472393A (en) * | 1944-09-25 | 1949-06-07 | American Steel & Wire Co | Process and bath for copper coating ferrous metal |
US2454610A (en) * | 1946-08-13 | 1948-11-23 | Narcus Harold | Method for metalization on nonconductors |
US3725108A (en) * | 1969-03-05 | 1973-04-03 | Enthone | Chemical reduction metal plated diallylphthalate polymer and preparation process |
US3682671A (en) * | 1970-02-05 | 1972-08-08 | Kollmorgen Corp | Novel precious metal sensitizing solutions |
US3674517A (en) * | 1970-07-23 | 1972-07-04 | Ppg Industries Inc | Solution for depositing transparent metal films |
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
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GB2232168B (en) * | 1989-05-01 | 1993-06-16 | Enthone | Circuit boards |
US5498467A (en) * | 1994-07-26 | 1996-03-12 | W. L. Gore & Associates, Inc. | Process for preparing selectively conductive materials by electroless metal deposition and product made therefrom |
US5731073A (en) * | 1996-10-01 | 1998-03-24 | W. L. Gore & Associates, Inc. | Reusable, selectively conductive, Z-axis, elastomeric composite substrate |
US5886413A (en) * | 1996-10-01 | 1999-03-23 | Gore Enterprise Holdings, Inc. | Reusable, selectively conductive, z-axis elastomeric composite substrate |
US20040110374A1 (en) * | 2002-12-10 | 2004-06-10 | Enthone, Inc. | Copper activator solution and method for semiconductor seed layer enhancement |
US6875260B2 (en) * | 2002-12-10 | 2005-04-05 | Enthone Inc. | Copper activator solution and method for semiconductor seed layer enhancement |
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Owner name: AMP-AKZO CORPORATION, A CORP. OF DE, DELAWARE Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:KOLLMORGEN CORPORATION;REEL/FRAME:005889/0477 Effective date: 19911018 |